Supporting Information
1
H NMR Studies of Nickel(II) Co
mplexes Bound to Oligonucleotides:
A Novel Technique for Distinguishing the
Binding Locations of Metal Complexes in
DNA.
Authors:
Pratip K. Bhattacharya, Holly J. Lawson
§
and Jacqueline K. Barton*
Division of Chemistry and Chemical Engineering,
California Institute of Technology,
Pasadena, California 91125
§ Department of Chemistry,
State University of New York College at Fredonia,
Fredonia, New York 14063
Corresponding Author:
Jacqueline K. Barton
Email:
jkbarton@its.caltech.edu
2
Supporting Information Available:
S1.
Effects of [Ni(phen)
2
(dppz)]Cl
2
on the
I
H NMR spectrum of d(GTCGAC)
2
in 90/10
H
2
O/D
2
O at 4
°
C on a Varian Unity
PLUS
-600 NMR spectrometer. Shown is the
aromatic region. The DNA sample cont
ained 0.5 mM duplex, 5mM NaCl, 15 mM
sodium phosphate, pD 7.0 in 100% D
2
O. The free metal complex sample contained 0.2
mM [Ni(phen)
2
(phi)]Cl
2
in the same buffer. The chemical shifts are relative to TMSP at
4
°
C. The broadening effect was most pr
onounced on major groove protons like T2CH3,
GIH8 and G4H8 while the minor groove pr
otons A5H2, G1NH2 and G4NH2 remained
relatively unbroadened.
S2.
Effects of [Ni(phen)
2
(phi)]Cl
2
on the
I
H NMR spectrum of d(GTCGAC)
2
in D
2
O at 4
°
C on a Varian Unity
PLUS
-600 NMR spectrometer. Shown is the aromatic region. The
DNA sample contained 0.5 mM duplex, 5 mM
NaCl, 50 mM sodium phosphate, pD 7.0
in 100% D
2
O. The free metal complex samp
le contained 0.2 mM [Ni(phen)
2
(phi)]Cl
2
in
the same buffer. The chemical shifts are relative to TMSP at 4
°
C.
S3.
Effects of [Ni(phen)
2
(phi)]Cl
2
on the
I
H NMR spectrum of d(GTGC
AC)
2
in D
2
O at 4
°
C on a Varian Unity
PLUS
-600 NMR spectrometer. Shown is the aromatic region. The
DNA sample contained 0.5 mM duplex, 5 mM
NaCl, 50 mM sodium phosphate, pD 7.0
in 100% D
2
O. The free metal complex sample
contained 0.5 mM of [Ni(phen)
2
(phi)]Cl
2
in the same buffer. The chemical shifts are relative to TMSP at 4
°
C.
2+
N
NN
N
Ni
N
N
N
N
R= Metal/1000 base-pairs
5'G
T
CG
A
C3'
3'CAGCTG5'
S1
A5H2
G1/G4NH2
2+
Ni
N
N
N
N
H
N
N
H
R= Metal/1000 base-pairs
S2
5'G
T
CG
A
C3'
3'CAGCTG5'
2+
Ni
N
N
N
N
H
N
N
H
R= Metal/1000 base-pairs
S3
5'G
T
G
C
A
C3'
3'CAC
G
TG5'